Saturated polycarboxylic acid es



Patented May 23, 1939 2,159,008

UNITED STATES PATENT OFFICE SATURATED POLYCARBOXYLIC ACID ES- TERS OFZ-OHLOROALLYL ALCOHOL Gerald H. Coleman and Bartholdt C. Hadler,Midland, Mich., assignors to The Dow Chemical Company, Midland, Mich., acorporation of Michigan No Drawing. Application March 14, 1938, SerialNo. 195,852

6 Claims. (Cl. 260485) compounds and as modifying agents in thepolydrop-wise to facilitate the distillation of water. merization ofvinyl compounds, particularly sty- The reacted mixture was cooled,washed with a rene. They vary in physical characteristics from per centaqueous sodium bicarbonate solution crystalline solids to high-boilingliquids and are and water, and the benzene removed by distillasoluble'in a number of organic solvents; e. g., tion. The ester product wasdecolorized with acetone, petroleum ether, etc. charcoal and, aftercrystallization from petro- The term saturated polycarboxylic acid asleum ether, was obtained as a white crystalline herein employed will beunderstood to include solid having a melting point of approximatelyoxalic acid and acids having the general formula 54.5-55.5 C. It has theformula:

R- (COOH)n 01 H H 01 wherein R. represents an aromatic, aliphatic, or 2cycloaliphatic hydrocarbon radical containing no E Z ethylenic linkages,and n represents an integer. mmp e 2 Examples of such acids are malonicacid, succinic A mixture of 118.0 grams (1.0 mole) of succinic acid,adipic acid, phthalic acid, methylsuccinic acid and 231.0 grams (2.5moles) of 2-chloroallyl acid, tricarballylic acid,naphthalene-1.2-dicaralcohol was heated at 50-56 C. for 24 hours.boxylic acid, hexahydrophthalic acid, cyclopen- During the heatingmethylene chloride was added tane dicarboxylic acid, etc. drop-wise tofacilitate the distillation of water The new esters may be prepared byesterifying from the mixture. The reacted mixture was 2-chloroa1lylalcohol with one of the acids herewashed with dilute aqueous sodiumbicarbonate 25 inbefore defined. The esterification is preferably So uton a W Methylene Chloride'WaS recarried out by heating a mixture of2-chloroallyl moved by distillation and the ester product fracalcoholand approximately one chemical equivationally distilled under vacuum.There was ob- "lent of the polycarboxylic acid at a temperature tained203 grams (73.7 per cent of the theoretical of approximately 50-120 C.It is also preferyield) of di-(2-chloroallyl) succinate, a pale able toemploy a small proportion, e. g., approxiyellow, slightly viscous liquiddistilling at 142- mately 0.01-0.04 molecular equivalent of a strong 145C. under 4 millimeters pressure, having a acid, such as sulphuric orbenzene sulphonic acid, specific grav y of 1261 at C-, and an ndex as acatalyst for the esterification. Water is of refraction, formed in thereaction and, if desired, a water- 4820 immiscible organic solvent, suchas benzene, tolnD uene, methylene chloride, etc., may be added for i thepurpose of promoting the vaporization and Di-(2-chloroallyl) succmatehas the formula. removal of the water in the form of an azeo- Cl 0 0 v01 tropic mixture with the solvent. Upon complen u g 40 tion of thereaction, the reacted mixture is treat- GH'=0*CHT()0 (OH9PG*OCH ed withsufficient alkali to neutralize the acid contained therein, after whichthe ester product Example 3 is separated by fractional distillationunder re- A i t of 73.0 grams 0 5 mole) of adipic d d p e e, y other DPODriate pr acid, 92.5 grams (1.0 mole) of 2-chloroallyl alco- V l hol,and 5 grams of benzene sulphonic acid was The following examples willillustrate a num-' heated t 33am; C for 3 hours, during which her ofWays in wh ch t e principle of 0111 inVentime benzene was added as inExample 1. Upon U011 has f e p y but e not to be 0011- completion of thereaction, the reacted mixture strued as llmltmg the same? was washedwith dilute sodium carbonate solu- Example 1 tion and the ester productseparated as in Example 2. There was obtained 92 grams (62 per A mixtureof 63.0 grams (0.5 mole) of oxalic cent of the theoretical yield) ofdi-(2-chloroacid dihydrate and 92.5 grams (1.0 mole) of 2- ally1-)adipate, a pale yellow liquid distilling at chloroallyl alcohol washeated at 82100 C. for 1'73175 C. under 4 millimeters pressure, hav-This invention concerns the esters of 2-chloroallyl alcohol withsaturated polycarboxylic acids. All such esters are new compounds usefulas intermediates in the preparation of other organic 4.25 hours in aflask fitted with dropping funnel, condenser, and receiver arranged insuch manner as to permit distillation of water from the mixture. Duringthe heating benzene was added ing a specific gravity of 1.193 at 20/4C., and having an index of refraction,

A mixture of 83.0 grams (0.5 mole) of phthalic acid, 92.5 grams (1.0mole) of 2-chloroallyl alcohol, and grams of benzene sulphonic acid washeated at-approximately 8090 C. for 20 hours as in Example 2. Thereacted mixture was washed and distilled as in Example 2, and the esterproduct was recovered as a light yellow liquid, distilling at 176-178 C.under 2 millimeters pressure, having a specific gravity of 1288' at20/4" 0., and having an index of refraction,

n=1.5373 Di-(2-chloroallyl-) phthalate has the formula:

oo11,( =o112 Other esters of the present class may be prepared byreacting 2-chloroallyl alcohol with an acid of the type hereinbeforedefined. For example, 2-chloroallyl alcohol may be reacted withsym.-dimethylsuccinic acid to produce di- (2-chloroallyl)sym.-dimethylsuccinate; with pimelic acid to produce di-(2-chloroallyl)pimelate; with plained, change being made as regards the materialsemployed, provided the ingredients stated by any of the following claimsor the equivalent of such stated ingredients be employed.

We therefore particularly point out and distinctly claim as ourinvention:

1. A 2-chloroallyl ester of an acid selected from the class consistingof oxalic acid and acids having the general formula:

R(COOH) 11 wherein R represents a hydrocarbon radical of the classconsisting of aromatic, aliphatic, and cycloaliphatic radicalscontaining no ethylenic linkages, and n represents an integer.

2. An ester of 2-ch1oroallyl alcohol having the general formula:

01 (I11 GH2=( J-GH2O- -R -o-om-o=oi12 wherein R represents a hydrocarbonradical of the class consisting of aromatic, aliphatic andcycloaliphatic radicals containing no ethylenic linkages.

3. An ester of Z-chloroallyl alcohol having the general formula:

4. Di- (2-chloroallyl-) oxalate, a white crystalline solid having amelting point of approximately 54.5-55.5 C., and having the formula:

5. Di(2-chloroallyl-) succinate, a liquid distilling at approximately142-145 C. under 4 millimeters pressure, and having a specific gravityof 1.261 at 20/4= C. and the formula:

oHz=ooH1-o oHz 2oo-o1izo=orn 6. Di-(2-chloroallyl-) adipate, a liquiddistilling at approximately 1'73-175 C. under 4 millimeters pressure,and having a specific gravity of 1.193 at 20/4" C. and the formula:

GERALD H. COLEMAN. BARTHOLDT C. HADLER.

